Ancient relative and absolute ages for a basaltic meteorite: Implications for timescales of planetesimal accretion and differentiation

Asuka 881394 is a unique basaltic meteorite that originated in the crust of a differentiated planetesimal in the early Solar System. We present high precision Pb, Mg, and Cr isotopic compositions of bulk samples and mineral separates from this achondrite. A ²⁰⁷Pb-²⁰⁶Pb internal isochron obtained from the radiogenic pyroxene and whole-rock fractions of Asuka 881394 yields an absolute age of 4566.5 ± 0.2 Ma, which we consider to be the best estimate for the crystallization age of this basaltic achondrite. The ²⁶Al-²⁶Mg systematics show some evidence of disturbance, but 5 of the 6 analyzed whole-rock and mineral fractions define an isochron corresponding to a ²⁷Al/²⁶Al ratio of (1.28 ± 0.07) × 10⁻⁶. Comparison with the ²⁶Al-²⁶Mg and Pb-Pb systematics in the D’Orbigny achondrite translates to a ²⁶Al-²⁶Mg age of 4565.4 ± 0.2 Ma for Asuka 881394. The ⁵³Mn-⁵³Cr systematics in whole-rock, silicate and chromite fractions correspond to a ⁵³Mn/⁵⁵Mn ratio of (3.85 ± 0.23) × 10⁻⁶. Compared to the most precise ⁵³Mn-⁵³Cr and Pb-Pb systematics available for the D’Orbigny angrite, this translates to a ⁵³Mn-⁵³Cr age of 4565.3 ± 0.4 Ma; similarly, a comparison with the NWA 4801 angrite yields a ⁵³Mn-⁵³Cr age of 4565.5 ± 0.4 Ma, in agreement with the age obtained relative to D’Orbigny. While the ²⁶Al-²⁶Mg and ⁵³Mn-⁵³Cr ages appear to be concordant in Asuka 881394, these ages are ∼1 Ma younger than its ²⁰⁷Pb-²⁰⁶Pb age. This discordance might have been caused by one or more of several reasons, including differences in the closure temperatures for Pb versus Cr and Mg diffusion in their host minerals combined with slow cooling of the parent body as well as differential resetting of isotopic systems by a process other than volume diffusion, e.g., shock metamorphism. The ancient age of Asuka 881394 suggests that basaltic volcanism on its parent planetesimal occurred within ∼3 Ma of the formation of earliest solids in the Solar System, essentially contemporaneously with chondrule formation. This requires that the Asuka 881394 parent body was fully accreted within ∼500,000 yrs of Solar System formation.     

The U-Pb systematics of angrite Sahara 99555

Angrite Sahara 99555 (hereafter SAH), precisely dated by Baker et al. (Baker J., Bizzarro M., Wittig N., Connelly J. and Haack H. (2005) Early planetesimal melting from an age of 4.5662 Gyr for differentiated meteorites. Nature436, 1127-1131), has been proposed as a new reference point for the early Solar System timescale and for calculation of the revised minimum age of our Solar System. The Pb-Pb age of SAH of 4566.18 ± 0.14 Ma, reported by Baker et al., differs from the Pb-Pb age of D’Orbigny, another basaltic angrite, of 4564.42 ± 0.12 Ma (Amelin Y. (2008) U-Pb ages of angrites. Geochim. Cosmochim. Acta72, 221-232), despite the fact that the relative ⁵³Mn-⁵³Cr and ¹⁸²Hf-¹⁸²W ages of these meteorites are identical. Here I report U-Pb data for 21 whole rock and pyroxene fractions from SAH, analyzed using the same approach as D’Orbigny (Amelin, 2008). These fractions contain between 1.3 and 8.9 pg of total common Pb, slightly more than analytical blank. Measured ²⁰⁶Pb/²⁰⁴Pb ratios are between 625 and 2817 for D’Orbigny, blank-corrected ²⁰⁶Pb/²⁰⁴Pb ratios are between 1173 and 6675. Eight acid-washed whole rock fractions yielded an isochron age of 4564.86 ± 0.38 Ma, MSWD = 1.5. Data for pyroxene fractions plot mostly above the whole rock isochron, and do not form a linear array in ²⁰⁷Pb/²⁰⁶Pb vs. ²⁰⁴Pb/²⁰⁶Pb isochron coordinates. The ²⁰⁷Pb^∗/²⁰⁶Pb^∗ model dates of the pyroxene fractions vary from 4563.8 ± 0.3 to 4567.1 ± 0.5 Ma. The difference between whole rock and pyroxene U-Pb systematics may be a result of re-distribution of radiogenic Pb at a mineral grain scale several million years after crystallization. Complexities of Sm-Nd, Lu-Hf, and possibly ²⁶Al-²⁶Mg mineral systematics of SAH, described previously, may be related to the same process that caused the re-distribution of radiogenic Pb. Disturbance of isotopic chronometers renders SAH an imperfect anchor for the early Solar System timescale. The problems with age determination revealed by the studies of SAH call for greater attention in Pb-isotopic dating of angrites and other achondrites.     

Al-Mg dating of asteroidal magmatism in the young Solar System

We present high-precision Mg isotope data for most classes of basaltic meteorites including eucrites, mesosiderite silicate clasts, angrites and the ungrouped Northwest Africa (NWA) 2976 measured by pseudo-high-resolution multiple-collector inductively coupled plasma mass spectrometry and utilising improved techniques for chemical purification of Mg. With the exception of the angrites Angra dos Reis, Lewis Cliff (LEW) 86010, NWA 1296 and NWA 2999 and the diogenite Bilanga, which have either been shown to have young ages by other dating techniques or have low Al/Mg ratios, all bulk samples of basaltic meteorites have ²⁶Mg excesses (δ²⁶Mg^∗=+0.0135 to +0.0392‰). The ²⁶Mg excesses cannot be explained by analytical artefacts, cosmogenic effects or heterogeneity of initial ²⁶Al/²⁷Al, Al/Mg ratios or Mg isotopes in asteroidal parent bodies as compared to Earth or chondrites. The ²⁶Mg excesses record asteroidal melting and formation of basaltic magmas with super-chondritic Al/Mg and confirm that radioactive decay of short-lived ²⁶Al was the primary heat source that melted planetesimals. Model ²⁶Al-²⁶Mg ages for magmatism on the eucrite/mesosiderite, angrite and NWA 2976 parent bodies are 2.6-3.2, 3.9-4.1 and 3.5 Myr, respectively, after formation of calcium-aluminium-rich inclusions (CAIs). However, the validity of these model ages depends on whether the elevated Al/Mg ratios of basaltic meteorites result from magma ocean evolution on asteroids through fractional crystallisation or directly during partial melting. Mineral isochrons for the angrites Sahara (Sah) 99555 and D’Orbigny, and NWA 2976, yield ages of and , respectively, after CAI formation. Both isochrons have elevated initial δ²⁶Mg^∗ values. Given the brecciated and equilibrated texture of NWA 2976 it is probable that its isochron age and elevated initial δ²⁶Mg^∗(+0.0175±0.0034‰) reflects thermal resetting during an impact event and slow cooling on its parent body. However, in the case of the angrites the marginally elevated initial δ²⁶Mg^∗(+0.0068±0.0058‰) may reflect either δ²⁶Mg^∗ ingrowth in a magma ocean prior to eruption and crystallisation or in an older igneous protolith with super-chondritic Al/Mg prior to impact melting and crystallisation of these angrites, or partial internal re-equilibration of Mg isotopes after crystallisation. ²⁶Al-²⁶Mg model ages and an olivine + pyroxene + whole rock isochron for the angrites Sah 99555 and D’Orbigny are in good agreement with age constraints from ⁵³Mn-⁵³Cr and ¹⁸²Hf-¹⁸²W short-lived chronometers, suggesting that the ²⁶Al-²⁶Mg feldspar-controlled isochron ages for these angrites may be compromised by the partial resetting of feldspar Mg isotope systematics. Even when age constraints from the ²⁶Al-²⁶Mg angrite model ages or the mafic mineral + whole rock isochron are considered, the relative time difference between Sah 99555/D’Orbigny crystallisation and CAI formation cannot be reconciled with Pb-Pb ages for Sah 99555/D’Orbigny and CAIs, which are ca. 1.0 Myr too old (angrites) or too young (CAIs) for reasons that are not clear. This discrepancy might indicate that ²⁶Al was markedly lower (ca. 40%) in the planetesimal- and planet-forming regions of the proto-planetary disc as compared to CAIs, or that CAI Pb-Pb ages may not accurately date CAI formation, which might be better dated by the ¹⁸²Hf-¹⁸²W and ²⁶Al-²⁶Mg chronometers as 4568.3±0.7 (Burkhardt et al., 2008) and (herein), respectively, when mapped onto an absolute timescale using Pb-Pb ages for angrites.     

A combined Sm-Nd, Rb-Sr, and U-Pb isotopic study of Mg-suite norite 78238: Further evidence for early differentiation of the Moon

Lunar Mg-suite norite 78238 was dated using the Sm-Nd, Rb-Sr, and U-Pb isotopic systems in order to constrain the age of lunar magma ocean solidification and the beginning of Mg-suite magmatism, as well as to provide a direct comparison between the three isotopic systems. The Sm-Nd isotopic system yields a crystallization age for 78238 of 4334 ± 37 Ma and an initial value of −0.27 ± 0.74. The age-initial (T-I) systematics of a variety of KREEP-rich samples, including 78238 and other Mg-suite rocks, KREEP basalts, and olivine cumulate NWA 773, suggest that lunar differentiation was completed by 4492 ± 61 Ma assuming a Chondritic Uniform Reservoir bulk composition for the Moon. The Rb-Sr isotopic systematics of 78238 were disturbed by post-crystallization processes. Nevertheless, selected data points yield two Rb-Sr isochrons. One is concordant with the Sm-Nd crystallization age, 4366 ± 53 Ma. The other is 4003 ± 95 Ma and is concordant with an Ar-Ar age for 78236. The ²⁰⁷Pb-²⁰⁶Pb age of 4333 ± 59 Ma is concordant with the Sm-Nd age. The U-Pb isotopic systematics of 78238 yield linear arrays equivalent to younger ages than the Pb-Pb system, and may reflect fractionation of U and Pb during sample handling. Despite the disturbed nature of the U-Pb systems, a time-averaged μ (²³⁸U/²⁰⁴Pb) value of the source can be estimated at 27 ± 30 from the Pb-Pb isotopic systematics. Because KREEP-rich samples are likely to be derived from source regions with the highest U/Pb ratios, the relatively low μ value calculated for the 78238 source suggests the bulk Moon does not have an exceedingly high μ value.     

U-Pb ages of angrites

Precise U-Pb ages, determined with double spike (²⁰²Pb-²⁰⁵Pb) thermal ionization m1ass spectrometry, are reported for angrites Angra dos Reis (AdoR), Lewis Cliff 86010 (LEW), and D’Orbigny. Nineteen of 23 acid-washed pyroxene fractions from these meteorites and whole rock fractions from D’Orbigny contain between 0.5 and 1.3 pg of total common Pb, indistinguishable from analytical blank. Measured ²⁰⁶Pb/²⁰⁴Pb ratios in these fractions are between 6300 and 14,100 for AdoR, 1160-4500 for LEW, and 608-8500 for D’Orbigny. Blank-corrected ²⁰⁶Pb/²⁰⁴Pb ratios for all three meteorites vary from 2160 to over 100,000. These fractions yielded precise and reproducible ²⁰⁷Pb^∗/²⁰⁶Pb^∗ dates with the average values of 4557.65 ± 0.13 Ma for AdoR, 4558.55 ± 0.15 Ma for LEW, and 4564.42 ± 0.12 Ma for D’Orbigny. Pb-Pb isochrons including data with slightly elevated common Pb, and U-Pb upper concordia intercepts, yield similar dates. The implications of these new Pb-isotopic ages of angrites are threefold. First, they demonstrate that AdoR and LEW are not coeval, and the group of “slowly cooled” angrites is therefore genetically diverse. Second, the new age of LEW suggests an upward revision of ⁵³Mn-⁵³Cr “absolute” ages by 0.7 Ma. Third, a precise age of D’Orbigny allows consistent linking of the ⁵³Mn-⁵³Cr and ²⁶Al-²⁶Mg extinct nuclide chronometers to the absolute lime scale.     

Al-Mg systematics in D’Orbigny and Sahara 99555 angrites: Implications for high-resolution chronology using extinct chronometers

We report on an investigation of the ²⁶Al-²⁶Mg isotope systematics in the D’Orbigny and Sahara 99555 angrites. High precision Mg isotope compositions and Al/Mg ratios were measured in mineral separates and whole rock samples from D’Orbigny and Sahara 99555 using multiple-collector inductively coupled plasma mass spectrometry (MC-ICPMS). Plagioclase separates from both angrites have resolvable excesses in ²⁶Mg (Δ²⁶Mg) that correlate with their respective Al/Mg ratios. ²⁶Al-²⁶Mg systematics in the mineral separates and whole rocks define precise isochrons that correspond to ²⁶Al/²⁷Al ratios of (5.06 ± 0.92) × 10⁻⁷ and (5.13 ± 1.90) × 10⁻⁷ and initial Δ²⁶Mg values of −0.006 ± 0.040‰ and −0.016 ± 0.047‰ for D’Orbigny and Sahara 99555, respectively. The slopes and initial Δ²⁶Mg values are identical for these two meteorites within errors and the data for both angrites considered together define an isochron corresponding to a ²⁶Al/²⁷Al ratio of (5.10 ± 0.55) × 10⁻⁷ and initial Δ²⁶Mg value of −0.012 ± 0.019. Relative to the Efremovka E60 CAI, the ²⁶Al/²⁷Al values reported here for these angrites imply ²⁶Al-²⁶Mg ages of 4562.42 ± 0.29 Ma and 4562.43 ± 0.53 Ma for D’Orbigny and Sahara 99555, respectively. These ²⁶Al-²⁶Mg ages are concordant with model ages determined using other extinct radionuclide chronometers (e.g., ⁵³Mn-⁵³Cr and ¹⁸²Hf-¹⁸²W), but are ∼2 Myr younger than the absolute ²⁰⁷Pb-²⁰⁶Pb ages that have been reported recently for these angrites. The reason for this discrepancy is not presently known, but may imply disturbance of one or more of the isotope systems under consideration or a possible bias in the ²⁰⁷Pb-²⁰⁶Pb ages of the angrites resulting from natural or analytical causes.     

Noble gases in D’Orbigny, Sahara 99555 and D’Orbigny glass—Evidence for early planetary processing on the angrite parent body

We analyzed the spallogenic, trapped, fissiogenic and radiogenic noble gas components in various bulk samples of the angrites D’Orbigny and Sahara 99555 as well as in glass separates of D’Orbigny. The D’Orbigny glass samples show hints of solar-like noble gases, as deduced from the trapped elemental and Ne isotopic compositions; the bulk samples do not contain detectable amounts of trapped gases. These observations indicate that D’Orbigny experienced a complex history shortly after its formation 4.56 Ga ago. The glass of D’Orbigny most likely represents magma that rose from the interior of the angrite parent body (APB) and was quenched near the surface. Hence, the APB may contain—similar to the interior of Earth and Mars—solar noble gases. This would call into question the suggested trapping mechanism for solar noble gases in the Earth and Mars, which involves the solution of early atmospheres into magma oceans, due to the APB’s inability to retain a primordial atmosphere. The first detection of—possibly parentless—radiogenic excess ¹²⁹Xe and solar noble gases in the glass of D’Orbigny indicates that the interior of APB degassed to a lesser degree than the outer regions. Therefore primordially trapped, fossil ¹²⁹I was kept. The APB was not completely devolatilized. Sahara 99555 yields a cosmic-ray exposure age of 6.8 ± 0.3 Ma, while D’Orbigny was exposed to cosmic rays for 11.9 ± 1.2 Ma. Both ages are different than those found in the other angrites. Hence, the angrites analyzed so far sampled surface material from the APB that was ejected in at least five events. In contrast to the bulk sample, the D’Orbigny glass separates yield concordant ages of only 3.0 ± 1.1 Ma, apparently suggesting a pre-exposure of the host material. However, such a scenario is unlikely, due to very similar Mn-Cr ages found in the bulk and glass of D’Orbigny. Most likely, this discrepancy is the result of additional, secondary gas-free glass. Such glass might have been formed during the meteorite’s entry into the Earth’s atmosphere. Isotopically anomalous Xe due to the decay of ²⁴⁷Cm has not been found. The presence of ²⁴⁷Cm in glass of D’Orbigny has been suggested based on Pb isotope constraints.     

Mineralogy, geochemistry, and Ar-Ar geochronology of lunar granulitic breccia Northwest Africa 3163 and paired stones: Comparisons with Apollo samples

The lunar meteorites Northwest Africa (NWA) 3163, 4881, and 4483 are paired stones classified as granulitic breccias. At 2.4 kg, these three stones constitute one of the largest known lunar meteorite masses. Here we describe the petrography, mineralogy, and chemistry of NWA 3163, 4881, and 4483, and present ⁴⁰Ar-³⁹Ar data for two of the meteorites. Two-pyroxene thermometry indicates that the rocks equilibrated at 1050 ± 50 °C, which represents the high-temperature, low-pressure event that generated their characteristic recrystallization textures and reset their Ar systematics. Stepped-heating, in situ infrared laser microprobe ⁴⁰Ar-³⁹Ar geochronology yields a mean age of 3327 ± 29 Ma for NWA 3163, and a more disturbed release spectrum for NWA 4881. NWA 4881 shows an upward-trending pattern, suggesting that it may have had a ⁴⁰Ar-³⁹Ar age of >3.0 Ga, but that it was partially reset at ∼2.6 Ga. NWA 3163 et al. exhibit shock effects, including maskelynitized plagioclase, shock veins, and melt pockets, which are absent in the Apollo granulitic breccias. Although the Apollo and meteorite samples are texturally similar and have comparable bulk compositions and equilibration temperatures, their trace and siderophile element contents point to distinct parental lithologies derived from different regions of the Moon. Based on mineralogical and geochemical differences between the Apollo and meteorite samples, we conclude that the parent rock(s) of the paired NWA meteorites came from an area outside the Imbrium region and that they underwent high-temperature (granulite event) metamorphism long after the Late Heavy Bombardment.     

Mechanisms for incompatible-element enrichment on the Moon deduced from the lunar basaltic meteorite Northwest Africa 032

The lunar meteorite Northwest Africa (NWA) 032 is a low-Ti basalt that has incompatible-element abundances and Th/Sm ratios characteristic of the involvement of late stage magma ocean crystallization products (urKREEP) in its petrogenesis. This sample is very fine-grained and contains terrestrial weather products. A progressive leaching procedure was therefore developed and applied to magnetic separates and whole rock fractions to obtain Rb-Sr and Sm-Nd ages. Although many of the leachates, as well as the unleached mineral and whole rock fractions contain terrestrial alteration products, selected residue fractions yield concordant Rb-Sr and Sm-Nd ages. Rubidium-Sr isotopic analyses yield an age of 2947 ± 16 Ma with an initial ⁸⁷Sr/⁸⁶Sr of 0.700057 ± 17. These characteristics indicate NWA 032 is derived from a source region with an ⁸⁷Rb/⁸⁶Sr ratio of 0.044 ± 0.001. This value is higher than all but those determined for KREEP basalts, and suggests that NWA 032 is derived from a source region that has higher incompatible-element abundances than other low-Ti basalts. Samarium-neodymium isotopic analysis yield a concordant age of 2931 ± 92 Ma and an initial ε_Nd of +9.71 ± 0.74 corresponding to a source region with ¹⁴⁷Sm/¹⁴⁴Nd ratio of 0.246 ± 0.004. The initial Nd isotopic composition stands in contrast to the initial Sr isotopic composition by requiring NWA 032 to be derived from a source with lower incompatible-element abundances than most low-Ti basalts. The source of NWA 032 is therefore unlike those of other lunar basalts.Modeling of magma ocean cumulate formation demonstrates that unlike other low-Ti basalt source regions the NWA 032 source is a mixture of olivine, pigeonite, and clinopyroxene bearing cumulates and only a small amount of urKREEP. Furthermore, unlike other mare basalt sources, the NWA 032 source does not contain appreciable quantities of plagioclase. Partial melting models demonstrate that the incompatible-element characteristics of the NWA 032 result from formation by smaller degrees of partial melting than other mare basalts. Thus, the incompatible-element geochemical signature that is observed in NWA 032 appears to reflect the combined effects of generation from an unusual plagioclase-free incompatible-element-depleted source region by very small degrees of partial melting. This study demonstrates that both the presence of urKREEP in the source region and small degrees of partial melting generate magmas with similar, but not identical, incompatible-element characteristics. In addition, it underscores the fact that there is significantly more geochemical diversity on the Moon than is represented by samples collected by the American and Soviet lunar missions.     

Concordant Rb-Sr, Sm-Nd, and Ar-Ar ages for Northwest Africa 1460: A 346 Ma old basaltic shergottite related to “lherzolitic” shergottites

Multiple lines of evidence show that the Rb-Sr, Sm-Nd, and Ar-Ar isotopic systems individually give robust crystallization ages for basaltic (or diabasic) shergottite Northwest Africa (NWA) 1460. In contrast to other shergottites, NWA 1460 exhibits minimal evidence of excess ⁴⁰Ar, thus allowing an unambiguous determination of its Ar-Ar age. The concordant Rb-Sr, Sm-Nd, and Ar-Ar results for NWA 1460 define its crystallization age to be 346 ± 17 Ma (2σ). In combination with petrographic and trace element data for this specimen and paired meteorite NWA 480, these results strongly refute the suggestion by others that the shergottites are ∼4.1 Ga old. Current crystallization and cosmic-ray exposure (CRE) age data permit identification of a maximum of nine ejection events for Martian meteorites (numbering more than 50 unpaired specimens as of 2008) and plausibly as few as five such events. Although recent high resolution imaging of the Martian surface has identified limited areas of sparsely cratered terrains, the meteorite data suggest that either these areas are representative of larger areas from which the meteorites might come, or that the cratering chronology needs recalibration. Time-averaged ⁸⁷Rb/⁸⁶Sr = 0.16 for the mantle source of the parent magma of NWA 1460/480 over the ∼4.56 Ga age of the planet is consistent with previously estimated values for bulk silicate Mars in the range 0.13-0.16, and similar to values of ∼0.18 for the “lherzolitic” shergottites. Initial ε_Nd for NWA 1460/480 at 350 ± 16 Ma ago was +10.6 ± 0.5, which implies a time-averaged ¹⁴⁷Sm/¹⁴⁴Nd of 0.217 in the Martian mantle prior to mafic melt extraction, similar to values of 0.211-0.216 for the “lherzolitic” shergottites. These time-averaged values do not imply a simple two-stage mantle/melt evolution, but must result from multiple episodes of melt extractions from the source regions. Much higher “late-stage” ε_Nd values for the depleted shergottites imply similar processes carried to a greater degree. Thus, NWA 1460/480, the “lherzolitic” shergottites and perhaps EET 79001 give the best (albeit imperfect) estimate of the Sr- and Nd-isotopic characteristics of bulk silicate Mars.     

Ar-Ar and I-Xe ages and thermal histories of three unusual metal-rich meteorites

Portales Valley, Sombrerete, and Northwest Africa (NWA) 176 are three unrelated meteorites, which consist of silicate mixed with substantial amounts of metal and which likely formed at elevated temperatures as a consequence of early impacts on their parent bodies. Measured ³⁹Ar-⁴⁰Ar ages of these meteorites are 4477 ± 11 Ma and 4458 ± 16 Ma (two samples of Portales Valley), 4541 ± 12 Ma, and 4524 ± 13 Ma, respectively (Ma = million years; all one-sigma errors). The Ar-Ar data for Portales Valley show no evidence of later open system behavior suggested by some other chronometers. Measured ¹²⁹I-¹²⁹Xe ages of these three meteorites are 4559.9 ± 0.5 Ma, 4561.9 ± 1.0 Ma, and ∼4544 Ma, respectively (relative to Shallowater = 4562.3 ± 0.4 Ma). From stepwise temperature release data, we determined the diffusion characteristics for Ar and Xe in our samples and calculated approximate closure temperatures for the K-Ar and I-Xe chronometers. Adopting results and interpretations about these meteorites from some previous workers, we evaluated all these data against various thermal cooling models. We conclude that Portales Valley formed 4560 Ma ago, cooled quickly to below the I-Xe closure temperature, then cooled deep within the parent body at a rate of ∼4 °C/Ma through K-Ar closure. We conclude that Sombrerete formed 4562 Ma ago and cooled relatively quickly. NWA 176 likely formed and cooled quickly ∼4544 Ma ago, or later than formation times of most meteorite parent bodies. For all three meteorites, the Ar-Ar ages are in better agreement with I-Xe ages and preferred thermal models if we increase these Ar-Ar ages by ∼20 Ma. Such age corrections would be consistent with probable errors in ⁴⁰K decay parameters in current use, as suggested by others. The role of impact heating and possible disruption and partial reassembly of meteorite parent bodies to form some meteorites likely was an important process in the early solar system.     

Constraints on the U-Pb isotopic systematics of Mars inferred from a combined U-Pb, Rb-Sr, and Sm-Nd isotopic study of the Martian meteorite Zagami

Uranium-lead, Rb-Sr, and Sm-Nd isotopic analyses have been performed on the same whole-rock, mineral, and leachate fractions of the basaltic martian meteorite Zagami to better constrain the U-Pb isotopic systematics of martian materials. Although the Rb-Sr and Sm-Nd systems define concordant crystallization ages of 166 ± 6 Ma and 166 ± 12 Ma, respectively, the U-Pb isotopic system is disturbed. Nevertheless, an age of 156 ± 6 Ma is derived from the ²³⁸U-²⁰⁶Pb isotopic system from the purest mineral fractions (maskelynite and pyroxene). The concordance of these three ages suggest that the ²³⁸U-²⁰⁶Pb systematics of the purest Zagami mineral fractions have been minimally disturbed by alteration and impact processes, and can therefore be used to constrain the behavior of U and Pb in the Zagami source region. The μ value of the Zagami source region can be estimated, with some confidence from the ²³⁸U-²⁰⁶Pb isochron, to be 3.96 ± 0.02. Disturbance of the U-Pb isotopic systems means that this represents a minimum value. The μ value of the Zagami source is significantly lower than the μ values estimated for most basaltic magma sources from Earth and the Moon. This is surprising given the high initial ⁸⁷Sr/⁸⁶Sr ratio (0.721566 ± 82) and low initial ε_Nd value (−7.23 ± 0.17) determined for Zagami that indicate that this sample is derived from one of the most highly fractionated reservoirs from any known planetary body. This suggests that Mars is characterized by a low bulk planet U/Pb ratio, a feature that is consistent with its relatively volatile-rich nature.The leachates contain terrestrial common Pb that was probably added to the meteorite during handling, curation, or sawing. The mineral fractions, particularly those with significant amounts of impact melt glass, contain a second contaminant. The presence of this contaminant results in Pb-Pb ages that are older than the crystallization age of Zagami, indicating that the contaminant is characterized by a high ²⁰⁷Pb/²⁰⁶Pb ratio. Such a contaminant could be produced by removal of single-stage Pb from a relatively high μ martian reservoir before ∼1.8 Ga, and therefore could be an ancient manifestation of hydrous alteration of martian surface material.     

The thermal history of the Acapulco meteorite and its parent body deduced from U/Pb systematics in mineral separates and bulk rock fragments

U/Pb systematics of the Acapulco meteorite have been determined on phosphate and feldspar separates and on grain size fractions of bulk material. The latter show an enrichment of U and Th with respect to CI chondrites and a low (∼1) Th/U ratio. This is consistent with the model that the majority of U and Th was added early by a low temperature melt to the Acapulco precursor. The feldspar exhibits a Pb isotope composition that is close to the primordial Pb composition. Mineral separates and bulk fractions define a ²⁰⁷Pb/²⁰⁶Pb isochron. The age corresponds to 4555.9 ± 0.6 Ma. This age anchors the thermal evolution of the Acapulco parent body into an absolute time scale. Evaluation of the Hf/W and U/Pb records with the cooling rates deduced from mineralogical investigations confirms the idea that the Acapulco parent body was fragmented during its cooling. The U/Pb system precisely dates this break-up at 4556 ± 1 Ma.     

Trace element systematics and Sm-Nd and Lu-Hf ages of Larkman Nunatak 06319: Closed-system fractional crystallization of an enriched shergottite magma

Combined ¹⁴⁷Sm-¹⁴³Nd and ¹⁷⁶Lu-¹⁷⁶Hf chronology of the martian meteorite Larkman Nunatak (LAR) 06319 indicates an igneous crystallization age of 193 ± 20 Ma (2σ weighted mean). The individual ¹⁴⁷Sm-¹⁴³Nd and ¹⁷⁶Lu-¹⁷⁶Hf internal isochron ages are 183 ± 12 Ma and 197 ± 29 Ma, respectively, and are concordant with two previously determined ¹⁴⁷Sm-¹⁴³Nd and ⁸⁷Rb-⁸⁷Sr internal isochron ages of 190 ± 26 Ma and 207 ± 14 Ma, respectively (Shih et al., 2009). With respect to the ¹⁴⁷Sm-¹⁴³Nd isotope systematics, maskelynite lies above the isochron defined by primary igneous phases and is therefore not in isotopic equilibrium with the other phases in the rock. Non-isochronous maskelynite is interpreted to result from shock-induced reaction between plagioclase and partial melts of pyroxene and phosphate during transformation to maskelynite, which resulted in it having unsupported ¹⁴³Nd relative to its measured ¹⁴⁷Sm/¹⁴⁴Nd ratio. The rare earth element (REE) and high field strength element (HFSE) compositions of major constituent minerals can be modeled as the result of progressive crystallization of a single magma with no addition of secondary components. The concordant ages, combined with igneous textures, mineralogy, and trace element systematics indicate that the weighted average of the radiometric ages records the true crystallization age of this rock. The young igneous age for LAR 06319 and other shergottites are in conflict with models that advocate for circa 4.1 Ga crystallization ages of shergottites from Pb isotope compositions, however, they are consistent with updated crater counting statistics indicating that young volcanic activity on Mars is more widespread than previously realized (Neukum et al., 2010).     

Ar-Ar ages of martian nakhlites

We report ³⁹Ar-⁴⁰Ar ages of whole rock (WR) and plagioclase and pyroxene mineral separates of nakhlites MIL 03346 and Y-000593, and of WR samples of nakhlites NWA 998 and Nakhla. All age spectra are complex and indicate variable degrees of ³⁹Ar recoil and variable amounts of trapped ⁴⁰Ar in the samples. Thus, we examine possible Ar-Ar ages in several ways. From consideration of both limited plateau ages and isochron ages, we prefer Ar-Ar ages of NWA 998 = 1334 ± 11 Ma, MIL 03346 = 1368 ± 83 Ma (mesostasis) and 1334 ± 54 Ma (pyroxene), Y-000593 = 1367 ± 7 Ma, and Nakhla = 1357 ± 11 Ma, (2σ errors). For NWA 998 and MIL 03346 the Ar-Ar ages are within uncertainties of preliminary Rb-Sr isochron ages reported in the literature. These Ar-Ar ages for Y-000593 and Nakhla are several Ma older than Sm-Nd ages reported in the literature. We conclude that the major factor in producing Ar-Ar ages slightly too old is the presence of small amounts of trapped martian or terrestrial ⁴⁰Ar on weathered grain surfaces that was degassed along with the first several percent of ³⁹Ar. A total K-⁴⁰Ar isochron for WR and mineral data from five nakhlites analyzed by us, plus Lafayette data in the literature, gives an isochron age of 1325 ± 18 Ma (2σ). We emphasize the precision of this isochron over the value of the isochron age. Our Ar-Ar data are consistent with a common formation age for nakhlites. The cosmic-ray exposure (CRE) age for NWA 998 of ∼12 Ma is also similar to CRE ages for other nakhlites.     

The Pb-Pb age of Angrite SAH99555 revisited

Representing a suite of well-preserved basaltic meteorites with reported ages from 4566.18 ± 0.14 Ma to 4557.65 ± 0.13 Ma, angrites have been recurring targets for cross-calibrating extinct and absolute chronometers. However, inconsistencies exist in the available chronological data set, including a 4566.18 ± 0.14 Ma Pb-Pb age reported by Baker et al. [Baker J., Bizzarro M., Wittig N., Connelly J. and Haack H. (2005) Early planetesimal melting from an age of 4.5662 Gyr for differentiated meteorites. Nature436, 1127-1131] for Sahara 99555 (herein SAH99555) that is significantly older than a Pb-Pb age for D’Orbigny, despite the two meteorites yielding indistinguishable Hf-W and Mn-Cr ages. We re-evaluate the Pb-Pb age of SAH99555 using a stepwise dissolution procedure on a whole rock fragment and a pyroxene separate. The combined data set yields a linear array that reflects a mixture of radiogenic Pb and terrestrial contamination and corresponds to an age of 4564.58 ± 0.14 Ma, which is 1.60 ± 0.20 Ma younger than that reported by Baker et al. [Baker J., Bizzarro M., Wittig N., Connelly J. and Haack H. (2005) Early planetesimal melting from an age of 4.5662 Gyr for differentiated meteorites. Nature436, 1127-1131]. Our conclusion that SAH99555 crystallized at 4564.58 ± 0.14 Ma requires that all initial Pb was removed in the first progressive dissolution steps, an assertion supported by linearity of data generated by stepwise dissolution of a single fragment and the removal of an obvious highly-radiogenic component early in the dissolution process. We infer that the linear array defined by Baker et al. [Baker J., Bizzarro M., Wittig N., Connelly J. and Haack H. (2005) Early planetesimal melting from an age of 4.5662 Gyr for differentiated meteorites. Nature436, 1127-1131] and their older age reflects a ternary mixture of Pb with constant relative proportions of highly-radiogenic initial Pb and radiogenic Pb with varying amounts of a terrestrial contamination. This requires that the phase harboring the initial Pb is insoluble in 2 M HCl, the only acid applied to the samples by Baker et al. [Baker J., Bizzarro M., Wittig N., Connelly J. and Haack H. (2005) Early planetesimal melting from an age of 4.5662 Gyr for differentiated meteorites. Nature436, 1127-1131] prior to dissolution.     

Neutron capture records of mesosiderites and an iron meteorite

The Sm and Gd isotopic compositions of silicates from six mesosiderites (Dalgaranga, Estherville, Morristown, Northwest Africa (NWA) 1242, NWA 2932, and Vaca Muerta) and one iron meteorite (Udei Station) were determined to elucidate the cosmic-ray exposure records. All seven samples showed significant ¹⁵⁰Sm/¹⁴⁹Sm and ¹⁵⁸Gd/¹⁵⁷Gd isotopic shifts from neutron capture reactions corresponding to neutron fluences of (1.3-21.8) × 10¹⁵ n cm⁻². In particular, Vaca Muerta showed a significantly higher neutron fluences than the other six samples. The parameter for the degree of neutron thermalization (ε_Sm/ε_Gd) also showed a significant difference between Vaca Muerta (0.76) and the other samples (0.93-1.20). These results suggest a two-stage irradiation of the Vaca Muerta silicates in the parent body (>50 Ma) before formation of the mesosiderite and during its transit to Earth (138 Ma). This is consistent with the ⁸¹Kr-Kr cosmic-ray exposure age data of a Vaca Muerta pebble from a previous noble gas isotopic study.     

On early Solar System chronology: Implications of an heterogeneous spatial distribution of Al and Mn

Early Solar System chronology is usually built with the assumption that the distribution of short-lived radionuclides was homogeneous through the solar accretion disk. At present, there is no unambiguous evidence for a homogeneous distribution of short-lived radionuclides in the solar accretion disk, while some data point to a heterogeneous distribution of short-lived radionuclides. In this paper, we explore a possible chronology based on a heterogeneous distribution of ²⁶Al and ⁵³Mn in the accretion disk. Our basic assumption is that the different abundances of extinct short-lived radionuclides in calcium-aluminium-rich inclusions (CAIs) and chondrules are due to spatial rather than temporal differences. We develop a simple model where CAIs and chondrules form contemporaneously, in different spatial locations, and are characterised by distinct initial ²⁶Al and ⁵³Mn abundances. In this model, all evolved bodies are supposed to be originally chondritic, i.e., to be made of a mixture of CAIs, chondrules, and matrix. This mixture determines the initial content in ²⁶Al and ⁵³Mn of a chondritic parent-body as a function of its CAI and chondrule abundance fraction. This approach enables us to calculate coherent ²⁶Al and ⁵³Mn ages from the agglomeration of the parent-body precursors (CAIs and chondrules) until the isotopic closure of ²⁶Al and ⁵³Mn, thereafter called ²⁶Al-⁵³Mn age. We calculate such ²⁶Al-⁵³Mn ages for a diversity of evolved objects, with the constraint that they should be found for realistic chondritic parent-body precursors, i.e., objects having similar or identical petrograpy to the existing chondrite groups. The so defined age of the d’Orbigny angrite is 4.3 ± 1.1 Myr, for the Asuka-881394 eucrite 2.8 ± 1.0 Myr, for the H4 chondrite Sainte Marguerite ∼3 Myr, and for H4 Forest Vale ∼5 Myr. The calculated ²⁶Al-⁵³Mn ages give timescales for the evolution of the respective parent-bodies/meteorites that can be investigated in the light of further petrographic studies. We anchor the calculated relative chronology to an absolute chronology using absolute Pb-Pb ages and relative Hf-W ages of the objects under scrutiny. The precursors of Sainte Marguerite and Forest Vale agglomerated at the same time (∼4565.8 ± 1.2 Ma ago). The precursors of eucrites (Asuka-881394) agglomerated 4564.8 ± 1.2 Ma ago. The precursors of angrites agglomerated late (4561.5 ± 1.8 Ma ago). Our model provides a fully compatible Al-Mg/Mn-Cr/Pb-Pb chronology, and is shown to be robust to reasonable changes in the input parameters. The calculated initial ²⁶Al/²⁷Al ratios are high enough to have ²⁶Al as a possible heat source for differentiation.     

Hf-W mineral isochron for Ca,Al-rich inclusions: Age of the solar system and the timing of core formation in planetesimals

Application of ¹⁸²Hf-¹⁸²W chronometry to constrain the duration of early solar system processes requires the precise knowledge of the initial Hf and W isotope compositions of the solar system. To determine these values, we investigated the Hf-W isotopic systematics of bulk samples and mineral separates from several Ca,Al-rich inclusions (CAIs) from the CV3 chondrites Allende and NWA 2364. Most of the investigated CAIs have relative proportions of ¹⁸³W, ¹⁸⁴W, and ¹⁸⁶W that are indistinguishable from those of bulk chondrites and the terrestrial standard. In contrast, one of the investigated Allende CAIs has a lower ¹⁸⁴W/¹⁸³W ratio, most likely reflecting an overabundance of r-process relative to s-process isotopes of W. All other bulk CAIs have similar ¹⁸⁰Hf/¹⁸⁴W and ¹⁸²W/¹⁸⁴W ratios that are elevated relative to average carbonaceous chondrites, probably reflecting Hf-W fractionation in the solar nebula within the first ∼3 Myr. The limited spread in ¹⁸⁰Hf/¹⁸⁴W ratios among the bulk CAIs precludes determination of a CAI whole-rock isochron but the fassaites have high ¹⁸⁰Hf/¹⁸⁴W and radiogenic ¹⁸²W/¹⁸⁴W ratios up to ∼14 ε units higher than the bulk rock. This makes it possible to obtain precise internal Hf-W isochrons for CAIs. There is evidence of disturbed Hf-W systematics in one of the CAIs but all other investigated CAIs show no detectable effects of parent body processes such as alteration and thermal metamorphism. Except for two fractions from one Allende CAI, all fractions from the investigated CAIs plot on a single well-defined isochron, which defines the initial ε¹⁸²W = −3.28 ± 0.12 and ¹⁸²Hf/¹⁸⁰Hf = (9.72 ± 0.44) × 10⁻⁵ at the time of CAI formation. The initial ¹⁸²Hf/¹⁸⁰Hf and ²⁶Al/²⁷Al ratios of the angrites D’Orbigny and Sahara 99555 are consistent with the decay from initial abundances of ¹⁸²Hf and ²⁶Al as measured in CAIs, suggesting that these two nuclides were homogeneously distributed throughout the solar system. However, the uncertainties on the initial ¹⁸²Hf/¹⁸⁰Hf and ²⁶Al/²⁷Al ratios are too large to exclude that some ²⁶Al in CAIs was produced locally by particle irradiation close to an early active Sun. The initial ¹⁸²Hf/¹⁸⁰Hf of CAIs corresponds to an absolute age of 4568.3 ± 0.7 Ma, which may be defined as the age of the solar system. This age is 0.5-2 Myr older than the most precise ²⁰⁷Pb-²⁰⁶Pb age of Efremovka CAI 60, which does not seem to date CAI formation. Tungsten model ages for magmatic iron meteorites, calculated relative to the newly and more precisely defined initial ε¹⁸²W of CAIs, indicate that core formation in their parent bodies occurred in less than ∼1 Myr after CAI formation. This confirms earlier conclusions that the accretion of the parent bodies of magmatic iron meteorites predated chondrule formation and that their differentiation was triggered by heating from decay of abundant ²⁶Al. A more precise dating of core formation in iron meteorite parent bodies requires precise quantification of cosmic-ray effects on W isotopes but this has not been established yet.     

Shock implantation of Martian atmospheric argon in four basaltic shergottites: A laser probe Ar/Ar investigation

Spatially resolved argon isotope measurements have been performed on neutron-irradiated samples of two Martian basalts (Los Angeles and Zagami) and two Martian olivine-phyric basalts (Dar al Gani (DaG) 476 and North West Africa (NWA) 1068). With a ∼50 μm diameter focused infrared laser beam, it has been possible to distinguish between argon isotopic signatures from host rock (matrix) minerals and localized shock melt products (pockets and veins). The concentrations of argon in analyzed phases from all four meteorites have been quantified using the measured J values, ⁴⁰Ar/³⁹Ar ratios and K₂O wt% in each phase. Melt pockets contain, on average, 10 times more gas (7-24 ppb ⁴⁰Ar) than shock veins and matrix minerals (0.3-3 ppb ⁴⁰Ar). The ⁴⁰Ar/³⁶Ar ratio of the Martian atmosphere, estimated from melt pocket argon extractions corrected for cosmogenic ³⁶Ar, is: Los Angeles (∼1852), Zagami (∼1744) and NWA 1068 (∼1403). In addition, Los Angeles shows evidence for variable mixing of two distinct trapped noble gas reservoirs: (1) Martian atmosphere in melt pockets, and (2) a trapped component, possibly Martian interior (⁴⁰Ar/³⁶Ar: 480-490) in matrix minerals. Average apparent ⁴⁰Ar/³⁹Ar ages determined for matrix minerals in the four analyzed meteorites are 1290 Ma (Los Angeles), 692 Ma (Zagami), 515 Ma (NWA 1068) and 1427 Ma (DaG 476). These ⁴⁰Ar/³⁹Ar apparent ages are substantially older than the ∼170-474 Ma radiometric ages given by other isotope dating techniques and reveal the presence of trapped ⁴⁰Ar. Cosmic ray exposure (CRE) ages were measured using spallogenic ³⁶Ar and ³⁸Ar production. Los Angeles (3.1 ± 0.2 Ma), Zagami (2.9 ± 0.4 Ma) and NWA 1068 (2.0 ± 0.5 Ma) yielded ages within the range of previous determinations. DaG 476, however, yielded a young CRE age (0.7 ± 0.25 Ma), attributed to terrestrial alteration. The high spatial variation of argon indicates that the incorporation of Martian atmospheric argon into near-surface rocks is controlled by localized glass-bearing melts produced by shock processes. In particular, the larger (mm-size) melt pockets contain near end-member Martian atmospheric argon. Based on petrography, composition and argon isotopic data we conclude that the investigated melt pockets formed by localized in situ shock melting associated with ejection. Three processes may have led to atmosphere incorporation: (1) argon implantation due to atmospheric shock front collision with the Martian surface, (2) transformation of an atmosphere-filled cavity into a localized melt zone, and (3) shock implantation of atmosphere trapped in cracks, pores and fissures.